GB2029850A - Reactive dyes their preparation and use - Google Patents
Reactive dyes their preparation and use Download PDFInfo
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- GB2029850A GB2029850A GB7920997A GB7920997A GB2029850A GB 2029850 A GB2029850 A GB 2029850A GB 7920997 A GB7920997 A GB 7920997A GB 7920997 A GB7920997 A GB 7920997A GB 2029850 A GB2029850 A GB 2029850A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
- C09B62/08—Azo dyes
- C09B62/09—Disazo or polyazo dyes
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Abstract
Reactive dyes of the formula <IMAGE> in which D1 is a benzene or naphthalene radical, which can be substituted, D2 is a benzene radical, which can be substituted, R1 is hydrogen or C1-4-alkyl, the bridge member -N(R1)- is bonded to a ring carbon atom of D2, R2 is hydrogen or C1-4-alkyl, which can be substituted, and R3 is hydrogen or substituted or unsubstituted alkyl, cycloalkyl, aralkyl or aryl.
Description
SPECIFICATION
Reactive dyes their preparation and use
The present invention relates to reactive dyes, their preparation and their use.
The invention provides reactive dyes of the formula
in which D, is a benzene or naphthalene radical, which can be substituted, D2 is a benzene radical, which can be substituted, R, is hydrogen or C, 4-alkyl, the bridge member -N(R,)- is bonded to a ring carbon atom of D2, R2 is hydrogen or C, 4-alkyl, which can be substituted, and
R3 is hydrogen or substituted or unsubstituted alkyl, cycloalkyl, aralkyl or aryl.
The radicals D, and D2 can contain the substituents customary in azo dyes. Examples of suitable further substituents are the following: alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl and butyl, alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy and butoxy, acylamino groups having 1 to 6 carbon atoms, such as acetylamino, propionylamino and benzoylamino, carbamoyl, sulfamoyl, amino groups, such as -N H2, methylamino and ethylamino, the ureido, hydroxyl and carboxyl group, halogen, such as fluorine, chlorine and bromine, and the sulfonic acid group.
The radicals D, and D2 contain in particular one or more sulfonic acid groups as further substituents. C, 4-alkyl R, can be: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl and tert.-butyl. An alkyl radical R2 can be substituted, for example by chlorine, hydroxyl, cyano, methoxy, carboxyl and sulfo.Examples of R2 are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl, tert.-butyl, sshydroxyethyl, ss-chloroethyl, ss-cyanoethyl, cyanomethyl, ycyanopropyl, ssmethoxyethyl, ffcarboxyethyl, sulfomethyl and fi-sulfoethyl. Examples of R3 are: hydrogen, the same substituted and unsubstituted alkyl radicals which have been mentioned above for R2, methoxypropyl, ethoxyethyl, ethyoxypropyl and methoxybutyl, cyclohexyl, benzyl, 4-sulfobenzyl, 4-methylbenzyl, phenethyl and in particular phenyl, which can be substituted by C, 4-alkyl, C, 4-alkoxy, acetylamino, ureido, carboxyl, halogen, sulfo, sulfomethyl, trifluoromethyl, sulfamoyl and carbamoyl, or naphthyl, which can be substituted by sulfo; R2 and R3 can also be closed to form a six-membered N-heterocyclic ring, which can contain a further heteroatom, such as nitrogen, oxygen and sulfur.Examples of the amino radical -NR2R3 in formula (1) are: -NH2, methylamino, ethylamino, propylamino, isopropylamino, butylamino, ss-methoxyethy- lamino, y-methoxypropylamino, N,N-dimethylamino, N,N-diethylamino, N-methyl-N-phenylamino, N-ethyl-N-phenylamino, P-chloroethylamino, P-hydroxyethylamino, y-hydroxypropylamino, benzylamino, cyclohexylamino, morpholino, piperidino, piperazino and, in particular, aromatic amino groups, such as phenylamino, toluidino, chloroanilino, anisidino, phenetidino, 2-, 3- and 4-sulfoanilino, 2,5-disulfoanilino, sulfomethylanilino, N-sulfomethylanilino, 3- and 4-carboxyphenylamino, 2-carboxy-5-sulfophenylamino, 2-carboxy-4-sulfophenylamino, 4-sulfonaphth- 1 -yl-am- ino, 3,6-disulfonaphth-l -yl-amino, 3,6,8-trisulfonaphth-1 -yl-amino and 4,6,8-trisulfonaphth-1 -yl- amino.
The disazo dyes of the formula (1) are fibre-reactive since they contain a detachable fluorine atom in the s-triazine radical.
Fibre-reactive compounds are to be understood as meaning those which are able to react with the hydroxyl groups of cellulose or with the amino groups of natural or synthetic polyamides with the formation of covalent chemical bonds.
The radical D, does not contain a reactive radical.
Preferred reactive dyes are those of the formula
in which one Y is hydrogen and the other Y is sulfo and D1, R2 and R3 are as defined under formula (1).
Preferred reactive dyes are especially those of the formula (2) in which D, is a benzene radical, which can be substituted by sulfo, methoxy and chlorine, or a naphthalene radical, which can be substituted by sulfo and nitro, R2 is hydrogen, methyl or ethyl and R3 is hydrogen, ethyl, sshydroxyethyl, butyl, phenyl, which can be substituted by methyl, methoxy, ethoxy, chlorine, acetylamino, ureido, carboxyl and sulfo, or naphthyl, which can be substituted by sulfo, or in which the amino group -NR2R3 is the morpholino radical.
Particularly preferred reactive dyes are those of the formula
in which R2 is hydrogen, methyl or ethyl and R2 is hydrogen or phenyl, which can be substituted by methyl, methoxy, chlorine and sulfo.
A valuable reactive dye of the category defined by formula (3) is the reactive dye of the formula
The preparation of the reactive dyes of the formula (1) comprises diazotisation, coupling and condensation reactions using a coupling component of the formula
a a diazo component of the formula D,N H2 (6), a further diazo component of the formula
2,4,6-trifluoro-s-triazine of the formula
and an amino compound of the formula
the said reactions being carried out in any order.
In a preferred embodiment the coupling component of the formula (5) which is used is a compound of the formula
in which one Y is hydrogen and the other Y is sulfo, and the diazo component of the formula (7) which is used is a compound of the formula
The starting materials used are in particular compounds of the formulae (6) and (9) in which
D, is a benzene radical, which can be substituted by sulfo, methoxy and chlorine, or a naphthalene radical, which can be substituted by sulfo and nitro, R2 is hydrogen, methyl or ethyl and R3 is hydrogen, ethyl, ss-hydroxyethyl, butyl, phenyl, which can be substituted by methyl, methoxy, ethoxy, chlorine, acetylamino, ureido, carboxyl and sulfo, or naphthyl, which can be substituted by sulfo, or in which the amino group -NR2R3 is the morpholino radical.
The preferred reactive dyes of the formula (3) are obtained by diazotisation, coupling and condensation reactions using a diazo component of the formula
1 amino-8-hydroxynaphthalene-3, 6-disulfonic acid, 1, 3-diaminobenzene-4-sulfonic acid, cyanuric fluoride and an amino compound of the formula (9), in which R2 and R3 are as defined under formula (3), the said reactions being carried out in any order.
Since the individual process steps indicated above, i.e. diazotisation, coupling and condensation, can be carried out in different orders, and, if desired, some process steps can also be carried out at the same time, various process variants are possible. The starting materials to be used for each partial reaction can be seen from formula (1). In general, the reaction is carried out in successive steps and the order in which the simple reactions between the individual reactants of the formulae (5) to (9) are carried out can be freely chosen.
Important process variants comprise 1. reacting a coupling component of the formula (5) with diazotised diazo components of the formulae (6) and (7) to give a disazo compound, subjecting the latter to a condensation reaction with 2,4,6-trifluoro-s-triazine of the formula (8) and subjecting the primary condensation product to a condensation reaction with an amino compound of the formula (9).
The last two reaction steps can also be carried out in a different order, by first subjecting the 2,4,6-trifluoro-s-triazine to a condensation reaction with an amino compound of the formula (9) and subjecting the resulting primary condensation product to a condensation reaction with the abovementioned disazo compound.
The procedure employed for the preparation of the abovementioned disazo compound is advantageously first to couple a diazotised diazo component of the formula (6) with a coupling component of the formula (5) and then to couple the resulting monoazo compound with a diazotised diazo component of the formula (7).
2. diazotising a diazo component of the formula (6) and coupling the resulting compound with a coupling component of the formula (5) and also subjecting 2,4,6-trifluoro-s-triazine of the formula (8) to a condensation reaction with an amino compound of the formula (9), subjecting the primary condensation product to a condensation reaction with a diazo component of the formula (7) and diazotising the resulting secondary condensation product and coupling the resulting product with the monoazo compound prepared initially.
The preferred procedure for the preparation of the reactive dye of the formula (4) comprises diazotising sulfanilic acid and 1 ,3-phenylenediamine-4-sulfonic acid and coupling the reaction product with 1 -amino-8-hydroxy-naphthalene-3, 6-disulfonic acid, subjecting the resulting intermediate of the formula
to a condensation reaction with cyanuric fluoride and subjecting the primary condensation product to a condensation reaction with m-chloroaniline.
The diazotisation of the diazo components is as a rule effected by the action of nitrous acid in aqueous-mineral acid solution at low temperature.
The coupling of the diazo component of the formula (6) with the coupling component of the formula (5) in the ortho-position relative to the H2N group is effected in strongly acid solution, at pH values of 1 to 2; the coupling of the diazo component of the formula (7) with the coupling component of formula (5) in the ortho-position relative to the HO group is effected in the weakly acid or neutral to weakly alkaline range, at pH values between 6.5 and 8.
In general, it is necessary first to carry out the coupling reaction in acid solution. In some cases, for the coupling reactions in which a diaminobenzenesulfonic acid is used as the diazo component of the formula (7), it is advantageous not to use this as itself, but, instead of this, to use an amino-acylamino-benzenesulfonic acid, for example 5-acetylaminoaniline-2-sulfonic acid, from which the acetyl group is detached by saponification after the coupling reaction has gone to completion, before carrying out the further condensation reaction. Furthermore, it is also possible to use a nitro-amino compound, for example 5-nitroaniline-2-sulfonic acid, as the diazo component of the formula (7) and, after the coupling reaction has taken place, to reduce the nitro group to the amino group with sodium sulfide or sodium hydrosulfide.
The condensation reactions of 2,4,6-trifluoro-s-triazine of the formula (8) with the diazo components of the formula (7) and the amino compounds of the formula (9) are preferably effected in aqueous solution or suspension, at low temperature and at a weakly acid or neutral to weakly alkaline pH value, so that at least one fluorine atom still remains as a detachable radical in the finished reactive dye of the formula (1). Advantageously, the hydrogen fluoride liberated during the condensation reaction is neutralised continuously by adding aqueous alkali metal hydroxides, alkali metal carbonates or alkali metal bicarbonates.
The preparation of the diazo intermediates is not described in all cases in the illustrative examples which follow, but is obvious from what has been stated above.
Examples of starting compounds for the preparation of the reactive dyes of the formula (1) are: (a) Coupling components of the formula (5) 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (H-acid), 1-amino-8-hydroxynaphthalene-4,6- disulfonic acid (K-acid) and 1-amino-8-hydroxynaphthalene-4-sulfonic acid.
(b) Diazo components of the formula (6) aniline, o-, m- and p-toluidines, o-, m- and p-anisidines, o-, m- and p-chloroanilines, 2,5dichloroaniline, a- and ss-naphthylamine, 2,5-dimethylaniline, 5-nitro-2-aminoanisole, 4-aminodiphenyl, aniline-2-, -3- and -4-carboxylic acids, 2-aminodiphenyl ether, 2-, 3- or 4-aminobenzenesulfonamide or 2-, 3- or 4-aminobenzenesulfonic acid mono-methyl- or -ethyl-amides or 2-, 3- or 4-aminobenzenesulfonic acid dimethyl- or diethyl-amides, aniline-2-, -3- and -4-sulfonic acid, aniline-2,5-disulfonic acid, 2,4-dimethyl-aniline-6-sulfonic acid, 4-chloro-5-methylaniline-2sulfonic acid, aniline-2,4-disulfonic acid, aniline-3,5-disulfonic acid, 2-amino-4- or -5-sulfobenzoic acid, 2-methylaniline-3,5-disulfonic acid, 2-methylaniline-5-sulfonic acid, 2-methoxyaniline3, 5-disulfonic acid, 2-chloroaniline-4-sulfonic acid, 2, 3-dimethylaniline-4, 6-disulfonic acid, 2,5dimethylaniline-4,6-disulfonic acid, 5-chloro-4-methylaniline-2-sulfonic acid, 3-acetylamino-aniline-6-sulfonic acid, 4-acetylaminoaniline-2-sulfonic acid, 4-chloroaniline-2-sulfonic acid, 3,4dichloroaniline-6-sulfonic acid, 4-methylaniline-2-sulfonic acid, 3-methylaniline-6-sulfonic acid, 2,4-dimethoxyaniline-6-sulfonic acid, 4-methoxyaniline-2-sulfonic acid, 5-methoxyaniline-2-sulfonic acid, 2, 5-dichloroaniline-4-sulfonic acid, 2,4-dimethylaniline-5-sulfonic acid, 2-methoxyaniline-5-sulfonic acid, 2-methylaniline-4-sulfonic acid, 4-nitroaniline-2-sulfuric acid, 4-ethoxyaniline-2-sulfonic acid, 4-ethylaniline-2-sulfonic acid, 4-acetylaminoaniline, 4-ethoxyaniline-3-sulfonic acid, 3,4-dichloroaniline, o-, m- and p-nitroaniline, m- and p-aminoacetanilide, 4-amino-2acetylaminotoluene-5-sulfonic acid, 4-methoxyaniline-3-sulfonic acid, 1-aminonaphthalene-2-, -4-, -5-, -6-, -7-or -8-sulfonic acid, 2-aminonaphthalene-1-, -5- or -6-sulfonic acid, 1-aminonaphthalene-3,6- or -5,7-disulfonic acid, 2-aminonaphthalene-1 ,5-, -1,7-, -3,6-, -5,7-, -4,8- or -6,8-disulfonic acid, 1 -aminonaphthalene-2,5, 7-trisulfonic acid, 2-aminonaphthalene-l ,5, 7-, -3,6,8- or -4,6, 8-trisulfonic acid, 1 -amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid, 2-amino
1 -hydroxynaphthalene-4, 8-disulfonic acid, 1 -amino-3-acetylaminobenzene (saponified), 1-amino
3-acetylaminobenzene-5- or -6-sulfonic acid (saponified), 1 -amino-4-acetylaminobenzene-2-sul
fonic acid (saponified), 1-amino-3-(N-acetyl-N-methylamino)-benzene (saponified), 3- or 4-nitroan
iline (reduced), 2-methoxy-4- or -5-nitroaniline (reduced), 2-methoxy-3-nitro-5-methylaniline
(reduced) and 2-methoxy-3-nitro-5-chloroaniline.
(c) Diazo components of the formula (7)
1,3- and 1,4-diaminobenzene, 1,3- and 1,4-diaminoanisole, 1,3and 1,4-diaminotoluene, 1,3
diamino-4-chlorobenzene, 1, 3-diamino-4-ethylbenzene, 1, 3-diamino-4-ethoxybenzene, 1,3-diam
inobenzene-4-sulfonic acid, 1 ,4-diaminobenzene-2-sulfonic acid, 1 ,4-diaminobenzene-2, 5-disul- fonic acid, 1 ,4-diaminobenzene-2, 6-disulfonic acid and 1, 3-diaminobenzene-4, 6-disulfonic acid.
(d) 2,4,6-Trifluoro-s-triazine of the formula (8) (cyanuric fluoride)
(e) Amino compounds of the formula (9)
ammonia, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, isopropylamine,
butylamine, dibutylamine, isobutylamine, sec.-butylamine, tert.-butylamine, hexylamine, methox
yethylamine, ethoxyethylamine, methoxypropylamine, chloroethylamine, hydroxyethylamine,
dihydroxyethylamine, hydroxypropylamine, aminoethanesulfonic acid, ,8-sulfatoethylamine, ben
zylamine, cyclohexylamine, aniline, o-, m- and p4oluidine, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5
dimethylaniline, o-, m- and p-chloroaniline, N-methylaniline, N-ethylaniline, 3- or 4-acetylami
noaniline, o-, m- and p-nitroaniline, o-, m- and p-aminophenol, 2-methyl-4-nitroaniline, 2-methyl
5-nitroaniline, 2, 5-dimethoxyaniline, 3-methyl-4-nitroaniline, 2-nitro-4-methylaniline, 3-nitro-4
methylaniline, o-, m- and p-anisidine, o-, m- and p-phenetidine, 2-methoxy-5-methylaniline, 2
ethoxy-5-methoxyaniline, 4-bromoaniline, 3-aminobenzamid, 4-aminophenylsulfamide, 3-trifluo
romethylaniline, 3- and 4-aminophenylurea, 1-naphthylamine, 2-naphthylamine, 2-amino-1 - hydroxy-naphthalene, 1-amino-4-hydroxy-naphthalene, 1 -amino-8-hydroxy-naphthalene, 1-am
ino-2-hydroxy-naphthalene, 1-amino-7-hydroxy-naphthalene, orthanilic acid, metanilic acid, sul
fanilic acid, aniline-2,4-disulfonic acid, aniline-2, 5-disulfonic acid, aniline-3,5-disulfonic acid,
anthranilic acid, m- and p-aminobenzoic acid, 4-aminophenylmethanesulfonic acid, aniline-N
methanesulfonic acid, 2-aminotoluene-4-sulfonic acid, 2-aminotoluene-5-sulfonic acid, p-amino
salicylic acid, 1 -am ino-4-carboxy-benzene-3-sulfonic acid, 1 -amino-2-carboxybenzene-5-sulfonic acid, 1-amino-5-carboxy-benzene-2-sulfonic acid, 1-naphthylamine-2-, -3-, -4-, -5-, -6-, -7- and
-8-sulfonic acid, 2-naphthylamine-1-, -3-, -4-, -5-, -6-, -7- and -8-sulfonic acid, 1-naphthylamine
2,4-, -2,5-, -2,7-, -2,8-, -3,5-, -3,6-, -3,7-, -3,8-, -4,6-, -4,7-, -4,8- and -5,8-disulfonic acid, 2
naphthylamine-1,5-, -1,6-, -1,7-, -3,6-, -3,7-, -4,7-, -4,8-, -5,7-and -6,8-disulfonic acid, 1
naphthylamine-2,4,6-, -2,4,7-, -2,5,7-, -3,5,7-, -3,6,8- and -4,6,8-trisulfonic acid, 2-naphthy
lamine-1,3,7-, -1,5,7-, -3,5,7-, -3,6,7-, -3,6,8- and -4,6,8-trisulfonic acid, 2-, 3- and 4
aminopyridine, 2-aminobenzthiazole, 5-, 6- and 8-aminoquinoline, 2-aminopyrimidine, morpho
line, piperidine and piperazine.
The reactive dyes of the formula (1) can be isolated and processed to usable, dry dye
preparations. Isolation is preferably effected at temperatures which are as low as possible, by
salting out and filtering. If desired, the dyes filtered off can be dried after adding diluents
and/or buffers, for example after adding a mixture of equal parts of monosodium phosphate and
disodium phosphate; preferably, drying is carried out at temperatures which are not too high
and under reduced pressure. In certain cases the dry preparations according to the invention can
be prepared direct, i.e. without intermediate isolation of the dyes, by spray-drying the entire
mixture in which they were prepared.
The reactive dyes of the formula (1) are novel. They are distinguished by high reactivity and
give dyeings which have good wet fastness properties and good fastness to light. Particular
mention should be made of the fact that the dyes have good solubility and electrolyte solubility
coupled with good uptake characteristics and good fixing of the dye, and that the portions not
fixed can be removed easily. The dyeings are dischargeable.
The reactive dyes of the formula (1) are suitable for dyeing and printing very diverse
materials, such as silk, leather, wool, high molecular weight polyamide fibres and high
molecular weight polyurethanes, but especially cellulose-containing materials of fibrous struc
ture, such as linen, cellulose, regenerated cellulose and in particular cotton. They are suitable
both for the exhaustion process and for dyeing by the pad dyeing method, according to which
the goods are impregnated with aqueous dye solutions, which can also contain salts, and the
dyes are fixed after an alkali treatment or in the presence of alkali, if necessary with the action
of heat.
They are also suitable for printing, especially of cotton, but are likewise also suitable for
printing nitrogen-containing fibres, for example wool, silk or mixed fabrics containing wool.
It is advisable to subject the dyeings and prints to thorough rinsing with cold and hot water, if necessary with the addition of an agent which acts as a dispersing agent and promotes the diffusion of the non-fixed portions.
In the following Examples parts are by weight and the temperatures are given in degrees
Centigrade.
Example 1
A neutral solution of 70.2 parts of the disazo dye of the formula
in 500 parts of water is cooled to O to 5"C by adding 300 parts of ice. 10 parts of cyanuric fluoride are allowed to run in in the course of 5 to 10 minutes, with vigorous stirring, and at the same time the pH of the reaction mixture is kept between 6 and 7 by the dropwise addition of 2
N sodium hydroxide solution. After the acylation has gone to completion, 10.7 parts of otoluidine are added to the solution of the difluorotriazine dye and the reaction mixture is warmed to 30 to 35"C and the pH is kept between 7 and 8 by dropwise addition of 2 N sodium hydroxide solution.After the reaction has gone to completion, 5 parts of disodium hydrogen phosphate are added to the solution of the monofluorotriazine dye and the solution is evaporated to dryness in a rotary evaporator at 40 to 45"C.
The dye thus obtained dyes cotton in navy blue shades.
Similar dyes, which also dye cotton in navy blue shades, are obtained when the above example is repeated using equivalent amounts of the amines listed below in place of o-toluidine.
Example Amines 2 m-Toluidine 3 p-Toluidine 4 2,4-Dimethylaniline 5 2,5-Dimethylaniline 6 2,6-Dimethylaniline 7 Ethanolamine 8 Aniline 9 N-Methylaniline
10 N-Ethylaniline
11 m-Chloroaniline 1 2 p-Chloroaniline
13 Acetyl-m-phenylenediamine
14 Acetyl-p-phenylenediamine
15 o-Anisidine 1 6 p-Anisidine 1 7 4-Aminophenyl-urea 1 8 3-Aminophenyl-urea 1 9 p-Aminobenzoic acid 20 Metanilic acid 21 2-Aminonaphthalene-6-sulfonic acid 22 Ammonia 23 m-Anisidine 24 4-Ethoxyaniline 25 Morpholine 26 Taurine
Further dyes, which dye cotton in the shades listed in column Ill, are obtained when the amino group-containing disazo dyes listed in column I are reacted with cyanuric fluoride and the amines listed in column II.
Example I ll Ill CI CI 'CI blue C o o o o NH2 - 2 1 =I = CDS CDD Z > D mS S 28 N=N o N=N 3-Aminotoluene blue = ' E c~ E SO3H H2N OH SO3H 29 CH3O N=N NN=N/\ n-Butylamine greenish-tinged - Q blue HO3S SO3H NH2 H2N OH SO3H 30 HO3S N N--N Aniline-3- greenish-tinged N SO3H sulfonic acid blue HO3S NH2 SO3H H2N OH SO3H 31 )%N1N N N/\ 4-Aminoanisole blue HO3S SO3 HNH2 HO3S ;t 2t ~ t) t f E x N cO a) o 11 N N N n n
Table cont.
t I ll Ill SO3H H2N OH SO3H m: o O: 32 1NN-NMNN-N/\ 3-Chloroaniline strongly greenish ra, i ra, ra, N O NH2 tinged blue SO3H O H2N O o c = ~ > > E 33 N H035 N SO3H Ethylamine blue-green SO3H SO3H H2N OH SO3H 34 1)N=NN-N/\ N-Methylaniline strongly greenish HO3S NH2 tinged blue SO3H SOCH H2 SO3H 35 N N-N A%N=N/\ 3-Aminotoluene strongly greenish S 9 tinged blue g mc 2 o 2A 9 ~ m ot Xot x N n t U) UJ 0) Table cont.
~ 2 c Q SO3H H2 NOH SO3H 36 N N=N N N=N\ Metanilic strongly greenish r0 02N HO3 S SO3H NH2 503H 37 HO3SN=N H$ OH SO3H Ammonia blue NH2 503H em f ~ 0N f O CL UJ Q CD Example 38
A neutral solution of 17.3 parts of orthanilic acid in 200 parts of water is cooled to 0 C by adding 250 parts of ice. 9 parts. of cyanuric fluoride are allowed to run in in the course of 10 minutes, with vigorous stirring, and the pH is kept between 6 and 7 by the dropwise addition of 2 N sodium hydroxide solution.When no further unchanged orthanilic acid is detectable, a neutral solution of 1 8.8 parts of m-phenylenediamine-sulfonic acid in 50 parts of water is added to the solution of the primary condensation product, the temperature is allowed to rise to 20 to 25"C and the pH of the reaction mixture is kept between 6.5 and 7.0. After the reaction has gone to completion, the secondary condensation product is salted out by adding 15% by volume of potassium chloride and filtered off.
25 parts of 4 N sodium nitrite solution are added to a neutral suspension of 45.6 parts of the secondary condensation product described above in 1 50 parts of water and the mixture is cooled to O to 5"C with ice. 30 parts of 10 N hydrochloric acid are added and after several hours the excess nitrite is destroyed with sulfamic acid.
The yellow suspension of the diazo compound which is thus obtained is then poured into an ice-cold neutral solution of 50.3 parts of the dye
acid "sulfanilic acid----,H-acid" in 1 50 parts of water, to which 30 parts of sodium bicarbonate have also been added prior to the coupling reaction.
A clear solution forms (volume about 750 parts) and the dye formed is salted out from this by adding 10% by volume of a mixture of sodium chloride and potassium chloride in a ratio of 1:1. After filtering, the dye paste is mixed with a concentrated aqueous solution of 5 parts of disodium hydrogen phosphate and dried in vacuo at 50"C.
The dye thus obtained dyes cotton in navy blue shades.
Example 39
10 parts of cyanuric fluoride are added dropwise in the course of about 10 minutes to an icecold, neutral solution of 1 7.3 parts of orthanilic acid in 400 parts of water, the pH value of the reaction mixture being kept between 6 and 7 by adding 1 N sodium hydroxide solution at the same time.
The primary condensation product thus obtained is then poured into a neutral solution of 70.2 parts of the disazo dye of the formula
in 500 parts of water and the reaction mixture is warmed to 30 to 35"C and the pH value is kept between 7 and 8 by the dropwise addition of 1 N sodium hydroxide solution.
After the acylation has gone to completion, 5 parts of disodium hydrogen phosphate are added to the solution of the monofluorotriazine dye and the solution is evaporated to dryness in a rotary evaporator at 40 to 45"C. The dye thus obtained dyes cotton in navy blue shades.
When the procedure of the above example is repeated except that 18.72 parts of 4aminotoluene-3-sulfonic acid are used in place of orthanilic acid, a dye is obtained which also dyes cotton in navy blue shades.
Example 40
2 parts of the dye obtained according to Example 1 are dissolved in 100 parts of water with the addition of 0.5 part of sodium m-nitrobenzenesulfonate. A cotton fabric is impregnated with the resulting solution so that the liquor pick-up is 75% and is then dried.
The fabric is then impregnated with a solution, at 20 , which contains, per litre, 5 grams of sodium hydroxide and 300 grams of sodium chloride, and squeezed off to a liquor pick-up of 75% and the dyeing is steamed for 30 seconds at 100 to 101", rinsed, soaped for a quarter of an hour in a 0.3% boiling solution of a non-ionic detergent, rinsed and dried.
Example 41
2 parts of the dye obtained according to Example 1 are dissolved in 100 parts of water.
The solution is added to 1,900 parts of cold water, 60 parts of sodium chloride are added and 100 parts of a cotton fabric are put into this dyebath.
The temperature is raised to 40 and after 30 minutes 4 parts by volume of 30% sodium hydroxide solution, 10 parts of calcined sodium carbonate and a further 60 parts of sodium chloride are added. The temperature is maintained at 40 for 30 minutes and the dyeing is then rinsed and soaped for 1 5 minutes in a 0.3% boiling solution of a non-ionic detergent, rinsed and dried.
Claims (18)
1. A reactive dye of the formula
in which D1 is a benzene or naphthalene radical, which can be substituted, D2 is a benzene radical, which can be substituted, R, is hydrogen or Ct 4-alkyl, the bridge member -N(R1)- is bonded to a ring carbon atom of D2, R2 is hydrogen or C1 4-alkyl, which can be substituted, and R3 is hydrogen or substituted or unsubstituted alkyl, cycloalkyl, aralkyl or aryl.
2. A reactive dye according to claim 1, of the formula
in which one Y is hydrogen and the other Y is sulfo and D1, R2 and R3 are as defined in claim 1.
3. A reactive dye according to claim 2, in which D1 is a benzene radical, which can be substituted by sulfo, methoxy and chlorine, or a naphthalene radical, which can be substituted by sulfo and nitro, R2 is hydrogen, methyl or ethyl and R3 is hydrogen, ethyl, sshydroxyethyl, butyl, phenyl, which can be substituted by methyl, methoxy, ethoxy, chlorine, acetylamino, ureido, carboxyl and sulfo, or naphthyl, which can be substituted by sulfo, or in which the amino group -NR2R3 is the morpholino radical.
4. A reactive dye according to claim 3, of the formula
in which R2 is hydrogen, methyl or ethyl and R3 is hydrogen or phenyl, which can be substituted by methyl, methoxy, chlorine and sulfo.
5. The reactive dye according to claim 4, of the formula
6. A reactive dye of formula I as defined in claim 1 substantially as described with reference to any of Examples 1 to 39.
7. A process for the preparation of a reaction dye of formula I according to claim 1 which comprises diazotisation, coupling and condensation reactions using a coupling component of the formula
a diazo component of the formula
D1-NH2 (6) wherein D1 is as defined in claim 1, a further diazo component of the formula
wherein R1 and D2 are as defined in claim 1, 2,4,6-trifluoro-s-triazine of the formula
and an amino compound of the formula
wherein R2 and R3 are as defined in claim 1, the said reactions being carried out in any order.
8. A process according to claim 7, wherein the coupling component of the formula (5) which is used is a compound of the formula
in which one Y is hydrogen and the other Y is sulfo, and the diazo component of the formula (7) which is used is a compound of the formula
9.A process according to claim 8, wherein the starting materials used are compounds of the formulae (6) and (9) in which D1 is a benzene radical, which can be substituted by sulfo, methoxy and chlorine, or a naphthalene radical, which can be substituted by sulfo and nitro, R2 is hydrogen, methyl or ethyl and R3 is hydrogen, ethyl, ss-hydroxyethyl, butyl, phenyl, which can be substituted by methyl, methoxy, ethoxy, chlorine, acetylamino, ureido, carboxyl and sulfo, or naphthyl, which can be substituted by sulfo, or in which the amino group -NR2R3 is the morpholino radical.
10. A process according to claim 9, for the preparation of a reactive dye of the formula
in which R2 is hydrogen, methyl or ethyl and R3 is hydrogen or phenyl, which can be substituted by methyl, methoxy, chlorine and sulfo, which comprises diazotisation, coupling and condensation reactions using a diazo component of the formula
1 -amino-8-hydroxynaphthalene-3, 6-disulfonic acid, 1, 3-diaminobenzene-4-sulfonic acid, cyanuric fluoride and an amino compound of the formula (9), in which R2 and R3 are as defined under formula (3), the said reactions being carried out in any order.
11. A process according to claim 10, for the preparation of the reactive dye of the formula
which comprises diazotising sulfanilic acid and 1 ,3-phenylenediamine-4sulfonic acid and coupling the reaction product with 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, subjecting the resulting intermediate of the formula
to a condensation reaction with cyanuric fluoride and subjecting the primary condensation product to a condensation reaction with m-chloroaniline.
12. A process for the preparation of a reactive dye of formula I, substantially as described with reference to any of Examples 1 to 39.
1 3. A reactive dye of formula I when produced by a process claimed in any of claims 7 to 12.
14. A method of dyeing or printing organic material wherein there is used a reactive dye as claimed in any of claims 1 to 6.
1 5. A method as claimed in claim 14 substantially as described with reference to Example 40 or 41.
16. Dyed or printed organic material when produced by a method claimed in claim 14 or 15.
1 7. A dyeing or printing preparation comprising a reactive dye as claimed in any of claims 1 to 6.
18. A dyeing or printing preparation as claimed in claim 1 7 substantially as described in
Examples 40 or 41.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH664678A CH638555A5 (en) | 1978-06-19 | 1978-06-19 | Reactive dyes and their preparation. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2029850A true GB2029850A (en) | 1980-03-26 |
| GB2029850B GB2029850B (en) | 1982-12-01 |
Family
ID=4312825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7920997A Expired GB2029850B (en) | 1978-06-19 | 1979-06-15 | Reactive dyes their preparation and use |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS55799A (en) |
| BE (1) | BE877051A (en) |
| BR (1) | BR7903817A (en) |
| CA (1) | CA1117938A (en) |
| CH (1) | CH638555A5 (en) |
| CS (1) | CS209926B2 (en) |
| DE (1) | DE2924228A1 (en) |
| ES (1) | ES481659A1 (en) |
| FR (1) | FR2429244A1 (en) |
| GB (1) | GB2029850B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4705524A (en) * | 1985-11-28 | 1987-11-10 | Hoechst Aktiengesellschaft | Mixtures of water-soluble fiber-reactive dyes and use thereof for dyeing: dioxazine and disazo dyes |
| US4839469A (en) * | 1985-04-13 | 1989-06-13 | Bayer Aktiengesellschaft | Reactive disazo dyestuffs having a fluorocontaining reactive group and a sulphatoethylsulphone substituent |
| US4872881A (en) * | 1987-06-30 | 1989-10-10 | Mitsubishi Kasei Corporation | Mixtures of water-soluble red and yellow or blue reactive dyes and a method of dyeing cellulosic fibers using such dye mixtures |
| CN101817996A (en) * | 2009-11-16 | 2010-09-01 | 天津德凯化工股份有限公司 | Reactive navy blue dyestuff for nylon dyeing |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3010161A1 (en) * | 1980-03-17 | 1981-09-24 | Bayer Ag, 5090 Leverkusen | DYES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR COLORING MATERIALS CONTAINING HYDROXYL GROUPS OR NITROGEN |
| DE3019960A1 (en) * | 1980-05-24 | 1981-12-03 | Hoechst Ag, 6000 Frankfurt | METHOD FOR COLORING AND PRINTING FIBER MATERIALS CONTAINING HYDROXY AND / OR CARBONAMIDE GROUPS |
| DE3151959A1 (en) * | 1981-12-30 | 1983-07-07 | Bayer Ag, 5090 Leverkusen | BISAZOREACTIVE DYES, METHOD FOR THEIR PRODUCTION AND THEIR USE FOR COLORING AND PRINTING FIBER MATERIAL CONTAINING HYDROXYL GROUPS OR NITROGEN |
| DE3317383A1 (en) * | 1983-05-13 | 1984-11-15 | Bayer Ag, 5090 Leverkusen | DISAZOREACTIVE DYES |
| GB8530024D0 (en) * | 1985-12-05 | 1986-01-15 | Ici Plc | Reactive dyes |
| JPS63112781A (en) * | 1986-10-27 | 1988-05-17 | 三菱化学株式会社 | Dyeing of cellulose-containing fibers |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH429986A (en) * | 1959-06-23 | 1967-02-15 | Ciba Geigy | Process for the production of organic dyes |
| CH400416A (en) * | 1960-09-01 | 1965-10-15 | Ciba Geigy | Process for the production of organic dyes |
| CH449818A (en) * | 1961-05-23 | 1968-01-15 | Ciba Geigy | Process for the preparation of new disazo dyes |
| GB961078A (en) * | 1961-05-23 | 1964-06-17 | Ciba Ltd | New disazo-dyestuffs and their manufacture and use |
| DE1644208C3 (en) * | 1967-04-19 | 1978-06-01 | Bayer Ag, 5090 Leverkusen | Reactive dyes |
| CH527258A (en) * | 1968-11-04 | 1972-08-31 | Ciba Geigy Ag | Process for the preparation of disazo compounds |
| CH626650A5 (en) * | 1974-12-18 | 1981-11-30 | Ciba Geigy Ag | |
| GB1515030A (en) * | 1976-02-11 | 1978-06-21 | Ici Ltd | Fibre reactive disazo dyestuffs |
-
1978
- 1978-06-19 CH CH664678A patent/CH638555A5/en not_active IP Right Cessation
-
1979
- 1979-06-15 DE DE19792924228 patent/DE2924228A1/en active Granted
- 1979-06-15 CS CS414279A patent/CS209926B2/en unknown
- 1979-06-15 CA CA000329891A patent/CA1117938A/en not_active Expired
- 1979-06-15 GB GB7920997A patent/GB2029850B/en not_active Expired
- 1979-06-18 BE BE0/195798A patent/BE877051A/en not_active IP Right Cessation
- 1979-06-18 FR FR7915605A patent/FR2429244A1/en active Granted
- 1979-06-18 ES ES481659A patent/ES481659A1/en not_active Expired
- 1979-06-18 BR BR7903817A patent/BR7903817A/en unknown
- 1979-06-19 JP JP7641479A patent/JPS55799A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4839469A (en) * | 1985-04-13 | 1989-06-13 | Bayer Aktiengesellschaft | Reactive disazo dyestuffs having a fluorocontaining reactive group and a sulphatoethylsulphone substituent |
| US4705524A (en) * | 1985-11-28 | 1987-11-10 | Hoechst Aktiengesellschaft | Mixtures of water-soluble fiber-reactive dyes and use thereof for dyeing: dioxazine and disazo dyes |
| US4872881A (en) * | 1987-06-30 | 1989-10-10 | Mitsubishi Kasei Corporation | Mixtures of water-soluble red and yellow or blue reactive dyes and a method of dyeing cellulosic fibers using such dye mixtures |
| CN101817996A (en) * | 2009-11-16 | 2010-09-01 | 天津德凯化工股份有限公司 | Reactive navy blue dyestuff for nylon dyeing |
Also Published As
| Publication number | Publication date |
|---|---|
| CH638555A5 (en) | 1983-09-30 |
| CA1117938A (en) | 1982-02-09 |
| ES481659A1 (en) | 1980-06-16 |
| FR2429244A1 (en) | 1980-01-18 |
| JPS6261622B2 (en) | 1987-12-22 |
| JPS55799A (en) | 1980-01-07 |
| CS209926B2 (en) | 1981-12-31 |
| DE2924228C2 (en) | 1990-02-15 |
| BE877051A (en) | 1979-12-18 |
| GB2029850B (en) | 1982-12-01 |
| DE2924228A1 (en) | 1979-12-20 |
| BR7903817A (en) | 1980-03-04 |
| FR2429244B1 (en) | 1983-10-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 732E | Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977) | ||
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19980615 |